Solid polymeric adhesive compositions having high use temperature, and articles and methods thereof

ABSTRACT

The teachings herein are directed at solid polymeric adhesive compositions for adhering metal components, methods for compounding the polymeric adhesive compositions, articles including a component having the polymeric adhesive composition, methods for producing articles including curing a solid adhesive, and articles including the cured adhesive. Preferred solid polymeric adhesive compositions include a plurality of one or more epoxy resins and one or more polysulfones. In one preferred aspect, the teachings are directed at a stator ring (e.g., for a hybrid motor) including the polymeric adhesive composition for adhering components to a ring.

CLAIM OF PRIORITY

The present patent application claims priority to U.S. ProvisionalPatent Application 62/425,326 filed on Nov. 22, 2016 and U.S.Provisional Patent Application 62/341,786 filed on May 26, 2016, eachincorporated herein by reference in its entirety.

FIELD

The teachings herein are directed at solid polymeric adhesivecompositions for adhering metal components, methods for compounding thepolymeric adhesive compositions, articles including a component havingthe polymeric adhesive composition, methods for producing articlesincluding curing a solid adhesive, and articles including the curedadhesive. Preferred solid polymeric adhesive compositions include aplurality of one or more epoxy resins and one or more polysulfones.

BACKGROUND

In order to reduce costs and/or improve performance, there is acontinuing need to provide multi-component parts that are adhered by anadhesive composition. In many applications, such as in automotive (e.g.,under the hood) applications, the ability to use specific adhesives arelimited by the service temperature. To adhere components in thesedemanding applications, there is a continuing need for improved adhesivecompositions.

Examples of epoxy adhesive compositions and epoxy compositions for usein applications such as prepregs for composites are described in U.S.Patent Application Publication No. US 2011/0048637, published on Mar. 3,2011, U.S. Pat. No. 6,063,839 A issued on May 16. 2000, and U.S. PatentApplication Publication No. US 2010/0280151, published on Nov. 4, 2010,U.S. Pat. No. 3,817,472 A issued on Jun. 25, 1974, and U.S. Pat. No.3,530,087 A issued on Sep. 22, 1970, incorporated herein by reference intheir entirety. Some of the compositions described in these referencesinclude epoxy resins and polysulfones. In many compositions, highconcentrations of liquid epoxy and/or low concentrations of thepolysulfone are included, and thus may have limited use as a solidadhesive part, which may be exposed to elevated temperatures duringshipping and storage (e.g., due to tackiness of the part). In somecompositions, the thermoplastic includes functional groups that mayreact with an epoxy group over time and limit the shelf life stabilityof the composition. Additionally, some compositions are employed incomposite applications with large amounts of fiber reinforcement whichprovide for stiffness at elevated temperature. However, processing ofthe adhesive composition (such as by extrusion or injection molding) isgenerally not possible after impregnating the fibers.

There continues to exist a need for polymeric adhesive compositions foradhering metal components for use in high temperature environments.There is also a need for such polymeric adhesive compositions that canbe extruded, molded, or otherwise formed in a part shaping machine priorto curing of the composition. There is also a need for polymericadhesive compositions which after curing have generally high tensilestrength at elevated temperature (e.g., a generally high ratio oftensile strength at elevated temperature to a tensile strength at roomtemperature). There is also a need for compositions that have good shelflife stability (e.g., prior to shaping into parts and/or prior toactivating by curing and/or expanding). There is also a need for apolymeric adhesive composition which can be expanded during the curingof the composition.

SUMMARY

One aspect of the teachings herein is directed at a polymeric adhesivecomposition (i.e., an activatable material) for molding or extruding anarticle comprising one or more epoxy resins (e.g., present in an amountof about 25 weight percent or more and/or about 85 weight percent orless, based on the total weight of the polymeric adhesive composition);about 7 to about 45 weight percent of one or more high temperaturethermoplastic polymers (based on the total weight of the polymericadhesive composition) having a glass transition temperature of about175° C. or more; about 0.5 to about 20 weight percent of one or moreimpact modifiers (e.g., present as an elastomeric polymer core in acore/shell polymer); one or more curatives for curing the epoxy resin(s)(e.g., in an amount from about 0.4 to about 15 weight percent, based onthe total weight of the polymeric adhesive composition); and optionallyup to 40 weight percent of one or more fillers; and optionally up toabout 7 weight percent (e.g., from about 0.1 to about 4 weight percent)of one or more blowing agents; wherein the one or more epoxy resinsincludes one or more solid epoxy resins and one or more liquid epoxyresins, wherein the concentration of the solid epoxy resin issufficiently high so that the polymeric adhesive composition is a solidat room temperature (e.g., the polymeric adhesive composition has atensile modulus of about 20 MPa or more, as measured according to ISO527 at about 23° C.).

Another aspect of the teachings is directed at a pre-cure articleincluding a polymeric adhesive composition according to the teachingsherein including one or more high glass transition temperaturethermoplastic resins and one or more epoxy resins.

Another aspect of the teachings is directed at a polymeric adhesivecomposition for molding or extruding an article comprising: about 35 toabout 65 weight percent of one or more epoxy resins, including a solidunmodified bisphenol-A based epoxy resin having an epoxide equivalentweight of about 800 g/equivalent or more as measured according to ISO3001, an epoxy cresol novolac resin having a functionality of about 3.5or more, and a liquid epoxy phenol novolac resin having an epoxyequivalent weight of about 150 to about 300 g/equivalent as measuredaccording to ISO 3001; about 12 to about 30 weight percent or more ofone or more thermoplastic polysulfones having a glass transitiontemperature of about 175° C. or more; about 1 to about 15 weight percentof one or more impact modifiers (e.g., an impact modifier that isincludes, consists essentially of, or consists entirely of a elastomericpolymer core of a core/shell polymer); about 2 to about 9 weight percentof one or more curatives for curing the epoxy resin(s), wherein the oneor more curatives includes a substituted urea; about 5 to about 25weight percent of one or more fillers selected from the group consistingof calcium carbonate, clay, and silica; about 0.1 to about 3 weightpercent rheology modifier (i.e., an organic or inorganic component thatincreases the viscosity of the activatable material, even when used atconcentrations of about 3 weight percent or less), and about 0.1 toabout 3 weight percent of one or more blowing agents; wherein the one ormore epoxy resins includes one or more solid epoxy resins and one ormore liquid epoxy resins, wherein the concentration of the solid epoxyresin is sufficiently high so that the polymeric adhesive composition isa solid at room temperature (e.g., the polymeric adhesive compositionhas a tensile modulus at room temperature of about 20 MPa or more, asmeasured according to ISO 527). The rheology modifier may be an organicor an inorganic material. The rheology modifier preferably is a plateshaped or fiber shaped material having an aspect ratio of about 3 ormore, preferably about 5 or more, and more preferably about 10 or more.An example of an organic rheology modifier is a polymeric fiber thatremains a solid at typical use temperatures and preferably remains asolid at typical processing temperatures. The organic rheology modifiermay include, consist essentially of, or consist entirely of polyaramidfibers (e.g., para-aramid fibers, such as KEVLAR® fibers). Preferredfibers for the rheology modifier have an average length of about 50 mmor less (e.g., about 35 mm or less);

Another aspect of the teachings relates to a device including a firstsubstrate (e.g., a metallic substrate) attached to a second substrate(e.g., a metallic substrate), wherein the first substrate and the secondsubstrate are directly attached by a polymeric adhesive component. Thepolymeric adhesive component may be formed from a polymeric adhesivecomposition including a blend of at least one or more solid epoxy resinsand at least one or more high glass transition temperature thermoplasticpolymers having a glass transition temperature of about 175° C. or more.Preferably, the polymeric adhesive composition is a polymeric adhesivecomposition according to the teachings herein. The polymeric adhesivecomponent may be formed by heating and curing the polymeric adhesivecomposition.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A and 1B are drawings of an illustrative lap shear test specimenfor testing an activatable material including a blowing agent. FIG. 1Aillustrates the geometry before expanding the activatable material, andFIG. 1B illustrates the geometry after expanding the activatablematerial (and trimming off any excess material).

FIG. 2 is a drawing of an illustrative lap shear test specimen fortesting an activatable material that is free of blowing agent.

FIG. 3 is a drawing of an illustrative part including two or morecomponents attached by a polymeric adhesive component (e.g., formed bycuring a polymeric adhesive composition according to the teachingsherein).

FIG. 4 is a perspective view illustrating features of a device includinga first component (e.g., a first substrate) that is adhered to two ormore second components (e.g., second substrates) by a polymeric adhesivecomponent (e.g., formed by curing a polymeric adhesive compositionaccording to the teachings herein).

FIG. 5 is a side view illustrating features of a device including afirst component that is attached to two or more teeth by a polymericadhesive component, where two adjacent teeth are in direct contact witheach other and/or directly adhered.

FIG. 6 is a side view illustrating features of a device including aplurality of teeth that are laterally nested and attached to a substrateby a polymeric adhesive component (e.g., formed by curing a polymericadhesive composition according to the teachings herein).

FIG. 7 is a perspective view from a side showing features of anillustrative device including a cylindrical shaped first substrate and aplurality of teeth attached to an interior surface of the firstsubstrate by a polymeric adhesive component (e.g., formed by curing apolymeric adhesive composition according to the teachings herein).

FIG. 8 is a side view showing a portion of the device illustrated inFIG. 7.

FIG. 9 is a perspective view from a side showing features of anillustrative device including a cylindrical shaped first substrate and aplurality of teeth attached to an interior surface of the firstsubstrate by a polymeric adhesive component (e.g., formed by curing apolymeric adhesive composition according to the teachings herein).

DETAILED DESCRIPTION

The polymeric adhesive compositions according to the teachings hereinare activatable materials, and includes one or more ingredients capableof polymerizing and/or cross-linking when heated. Additionally, theactivatable materials typically bonds to substrates upon being heated.The activatable material may also be capable of expanding upon heating.Preferably the bond is a durable bond that is maintained after exposureto heat, environmental conditions, and/or mechanical forces, such asexpected during use.

Unless otherwise specified, the term “consists substantially of” refersto a concentration of about 80 to 100 percent by weight, preferablyabout 90 to 100 percent by weight, more preferably from 95 to 100percent by weight, even more preferably from 98 to 100 percent byweight, and most preferably from 99.2 to 100 percent by weight.

The polymeric adhesive composition should be a solid material at ambientconditions. For example, the polymeric adhesive composition (i.e., inthe uncured state) may have a tensile modulus of about 20 MPa or more,preferably about 50 MPa or more, more preferably about 100 MPa or more,and most preferably about 200 MPa or more, as measured according to ISO527 at 23° C. (and preferably at about 50° C.). The polymeric adhesivecomposition may have a tensile modulus of about 1000 MPa or less, about600 MPa or less, or about 450 MPa or less, as measured according to ISO527 at 23° C.

The polymeric adhesive compositions herein preferably are capable ofbeing formed into pellets or other particles and stored as pelletswithout agglomeration. The pellets or other particles may later be fedinto a part shaping machine such as an extruder or an injection moldingmachine. The particles may be applied to a surface using a sprayingdevice.

High glass transition temperature thermoplastic polymer

The high glass transition temperature thermoplastic polymer may includeany thermoplastic polymer having a glass transition temperature of about175° C. or more. The high glass transition temperature thermoplasticpolymer may include one or more thermoplastic polymers selected from thegroup consisting of polysulfone, polyester sulfone, polyphenyl sulfone,polyetheretherketone, polyetherimide, copolymers thereof, andcombinations thereof. Preferably the high glass transition temperaturethermoplastic polymer includes a polysulfone homopolymer and/or apolysulfone copolymer. Preferred polysulfone homopolymers consistsubstantially of (e.g., about 99 weight percent or more, about 99.5weight percent or more, about 99.6 weight percent or more, or about 100weight percent), or entirely of a monomer repeat unit having one or moresulfone linkages. Preferred polysulfone copolymers include a firstmonomer repeat unit having one or more sulfone linkages, and one or moresecond monomers. Preferable monomer repeat units having a sulfonelinkage include a bisphenol A polysulfone repeat units (formula 1), apolyester sulfone repeat unit, a polyphenylene sulfone repeat unit, apolyether sulfone repeat unit, a polyphenylene ether sulfone repeatunit, or any combination thereof. The monomer repeat unit including asulfone linkage (for example the bisphenol A polysulfone repeat unit)may be present at a concentration of about 60 weight percent or more,about 75 weight percent or more, about 90 weight percent or more, about95 weight percent or more, or about 97 weight percent or more, based onthe total weight of the polysulfone copolymer. The concentration of thefirst monomer repeat unit (e.g., bisphenol A polysulfone repeat units)in the polysulfone copolymer may be about 99 weight percent or less, orabout 98 weight percent or less, based on the total weight of thecopolymer.

The high glass transition temperature thermoplastic polymer may have aglass transition temperature (e.g., as measured according todifferential scanning calorimetry at a heating rate of about 10° C./min)of about 175° C. or more, preferably about 180° C. or more, even morepreferably about 185° C. or more, and most preferably about 190° C. ormore. The high glass transition temperature thermoplastic polymer mayhave a glass transition temperature of about 280° C. or less, preferablyabout 250° C. or less, even more preferably about 240° C. or less, andmost preferably about 225° C. or less. For example, the high glasstransition temperature thermoplastic polymer may have a glass transitiontemperature from about 175° C. to about 280° C., from about 175° C. toabout 225° C., from about 185° C. to about 280° C., or from about 185°C. to about 225° C.

Although the polysulfone may be a functionalized polysulfone (e.g.,having an end group, such as an amine group capable of reacting with anepoxy resin), it is preferred that some or all of the polysulfonepolymer molecules are free of such functionalized groups. Preferably,the concentration of polysulfone polymer molecules having at least oneamine end group may be about 50 weight percent or less, about 20 weightpercent or less, about 10 weight percent or less, about 5 weight percentor less, about 2 weight percent or less or about 1 weight percent orless, based on the total weight of the polysulfone. The concentration ofthe polysulfone polymer molecules having at least one amine end groupmay be about 0 weight percent or more. For example, the polymericadhesive compositions according to the teachings herein may besubstantially free of or entirely free of block copolymers including apolysulfone molecule grafted with an epoxy molecule.

Preferably, some or all of the monomer repeat units of the polysulfoneincludes an ether linkage.

The polysulfone preferably has no amine groups or other nitrogen atoms(e.g., terminal amine groups or otherwise) that can react with an epoxygroup.

The monomer repeat unit including a sulfone linkage may be a bisphenol Apolysulfone repeat unit (or a derivative thereof), such as a monomerrepeat unit shown in Formula 1:

The monomer repeat unit including a sulfone linkage may be a polyestersulfone repeat unit (or a derivative thereof, such as a monomer repeatunit shown in Formula 2).

—[—O-Ph-SO₂—O-Ph—]—  (Formula 2)

The monomer repeat unit including a sulfone linkage may be apolyphenylene sulfone repeat unit (or a derivative thereof), such as amonomer repeat unit shown in Formula 3.

—[-Ph-SO₂—]—  (Formula 3)

The monomer repeat unit including a sulfone linkage may be a polyethersulfone repeat unit (or a derivative thereof), such as a monomer repeatunit shown in Formula 4 (e.g., POLYETHER SULFON Sulfon 200P™commercially available from IMPERIAL CHEMICAL INDUSTRIES).

—[-Ph-SO₂-Ph-O—]—  (Formula 4)

The monomer repeat unit including a sulfone linkage may have thestructure as shown in Formula 5 (or a derivative thereof).

—[—O—C(O)-Ph(CH₃)—C(O)—O-Ph-O-Ph-SO₂-Ph-O-Ph(CH3)-]—  (Formula 5)

The monomer repeat unit including a sulfone linkage may be apolyphenylene ether sulfone repeat unit (or a derivative thereof), suchas a monomer repeat unit shown in Formula 6.

—[-Ph-Ph-O-Ph(R)_(x)—SO₂-Ph(R)_(x)—O—]—  (Formula 6)

x is 0, 1, 2, 3, or 4; and each R is H, alkyl, aryl, akyl aryl, alkoxy,halogen, or any combination thereof.

As used herein, a derivative of the monomer repeat unit includes astructure where one or more Ph units is substituted with Ph(R)_(X)T,where x is 0, 1, 2, 3, or 4; and each R is independently H, alkyl, aryl,alkyl aryl, alkoxy, halogen, or a combination thereof.

The monomer repeat unit of the polysulfone polymer may include one ormore sulfone linkages, and optionally one or more linkages selected fromthe group consisting of one or more ester linkages, one or more phenyllinkages, and one or more isopropylene linkages. For example, themonomer repeat unit may include two aryl sulfone linkages.

High glass transition temperature polymer (e.g., polysulfone)properties:

The high glass transition temperature polymer (e.g., polysulfone)preferably has a viscosity in the molten or liquid state (e.g., at about343° C.) sufficient for mixing the polymer with at least a portion ofthe filler, at least a portion of the epoxy resin, or both. For example,the melt flow rate (in units of g/10 min as measured according to ASTMDD1238 at 343° C./2.16 kg) of the high glass temperature thermoplasticpolymer may be about 0.5 or more, preferably about 1 or more, even morepreferably about 2 or more, and most preferably about 3 or more. Themelt flow rate of the high glass transition temperature polymer shouldbe sufficiently low so that the polymer and/or the activatable materialhas good mechanical properties (e.g., at elevated temperatures). Themelt flow rate (in units of g/10 min as measured according to ASTMDD1238 at 343° C./2.16 kg) of the high glass transition temperaturethermoplastic polymer preferably is about 500 or less, more preferablyabout 100 or less, even more preferably about 55 or less, even morepreferably about 38 or less, and most preferably about 25 or less.

The activatable material preferably includes the high glass transitiontemperature thermoplastic polymer in an amount sufficient so that thetensile modulus decreases by less than about 50% upon heating the curedmaterial (e.g., cured at 175° C. for 30 minutes) from about 23° C. toabout 150° C. and/or from about 23° C. to about 170° C. Preferably thehigh glass transition temperature thermoplastic polymer is present in anamount of about 5 weight percent or more, more preferably about 7 weightpercent or more, even more preferably about 10 weight percent or more,even more preferably about 12 weight percent or more, and mostpreferably about 14 weight percent or more, based on the total weight ofthe polymeric adhesive composition. High glass transition temperaturethermoplastic polymers, such as polysulfones, are difficult to processand/or degrade at high processing temperatures. The polymeric adhesivecomposition preferably includes about 50 weight percent or less of thehigh glass transition temperature thermoplastic polymers (e.g., thepolysulfone), more preferably about 45 weight percent or less, even morepreferably about 40 weight percent or less, even more preferably about35 weight percent or less, and most preferably about 30 weight percentor less, based on the total weight of the polymeric adhesivecomposition.

The polymeric adhesive compositions according to the teaching hereininclude one or more epoxy resins for providing a durable adhesion tosubstrate after curing.

Epoxy resin is used herein to mean any of the conventional dimeric,oligomeric or polymeric epoxy materials containing at least one epoxyfunctional group. Moreover, the term epoxy resin can be used to denoteone epoxy resin or a combination of multiple epoxy resins. Thepolymer-based materials may be epoxy-containing materials having one ormore oxirane rings polymerizable by a ring opening reaction. Inpreferred embodiments, the polymeric adhesive composition includes up toabout 85 weight % or more of an epoxy resin. The total amount of theepoxy resin(s) may be about 85 weight % or less, about 80 weigh percentor less, about 75 weight percent or less, about 70 weight percent orless, about 65 weight percent or less, or about 60 weight percent orless, preferably based on the total amount of polymer in the polymericadhesive composition, and more preferably based on the total weight ofthe polymeric adhesive composition. The total amount of the epoxyresin(s) may be about 20 weight percent or more, about 25 weight percentor more, about 30 weight percent or more, about 35 weight percent ormore, or about 40 weight percent or more, preferably based on the totalweight of the polymeric adhesive composition, and more preferably basedon the total weight of the polymer in the polymeric adhesivecomposition. For example, the activatable material may include betweenabout 20% and about 85% by weight epoxy resin, between about 25% andabout 85% by weight epoxy resin, between about 30% and about 70 percentby weight, or between about 30% and even more preferably between about30% and 60% by weight epoxy resin, based on the total weight of theactivatable material. Of course, amounts of epoxy resin may be greateror lower depending upon the intended application of the activatablematerial. As an example, it is contemplated that weight percentages maybe lower or higher when other ingredients such as the adduct, filler,alternative polymers, combinations thereof or the like are used ingreater or lesser weight percentages.

The epoxy may be aliphatic, cycloaliphatic, aromatic or the like. Theepoxy may be supplied as a solid (e.g., as pellets, chunks, pieces orthe like) or a liquid (e.g., an epoxy resin). As used herein, unlessotherwise stated, a resin is a solid resin if it is solid at atemperature of 23° C. and is a liquid resin if it a liquid at 23° C. Theepoxy resin is added to the activatable material to increase theadhesion, flow properties or both of the material. The epoxy may includea copolymer including two or more monomers, or a terpolymer includingthree or more monomers. As a homopolymer, a copolymer or a terpolymer,the epoxy may include monomers with high chemical reactivity and thatare capable of linking up with similar molecules, resulting in anincrease in chain length and/or grafting and/or crosslinking. Typicallythe epoxy resin has a functionality of two or more, including a firstreactive site spaced apart from a second reactive site (e.g., atdifferent end of the chain). The functionality of the epoxy resintypically is about 10 or less, however, higher functionality may beemployed. Preferably at least a portion of the epxoy resin includes amultifunctional epoxy resin (i.e., having a functionality of greaterthan 2). The multifunctional epoxy resin preferably may have afunctionality of about 2.2 or more, about 2.5 or more, about 3 or more,about 3.5 or more, or about 4 or more. The multifunctional epoxy resinpreferably is present in the activatable material at a concentration ofabout 20 weight percent or more, more preferably about 40, even morepreferably about 50 weight percent or more, and most preferably about 55weight percent or more, based on the total weight of the one or moreepoxy resins in the activatable material. The amount of multifunctionalepoxy resin in the activatable material may be about 100 weight percentor less, preferably about 95 weight percent or less, more preferablyabout 90 weight percent or less, even more preferably about 85 weightpercent or less, and most preferably about 80 weight percent or less,based on the total weight of the one or more epoxy resins. One exemplaryepoxy resin may be a phenolic resin, which may be a novolac type orother type resin. For example, the multi-functional epoxy resin mayinclude, consist substantially of, or consist entirely of one or moreepoxy cresol novolac resins and/or one or more epoxy phenol novolacresins. Another preferred epoxy resin is a bisphenol-F epoxy resin.Other preferred epoxy containing materials may include a bisphenol-Aepichlorohydrin ether polymer, or a bisphenol-A epoxy resin which may bemodified with butadiene or another polymeric additive. Moreover, variousmixtures of several different epoxy resins may be employed as well.Examples of suitable epoxy resins are sold under the tradenamesARALDITE® (e.g., CT 6060, GT 6097, ECN 9699, and EPN 9850), commerciallyavailable from Huntsman Corporation, EPALLOY™ (e.g., 8250), commerciallyavailable from CVC Thermoset Specialties, and DER® (e.g., DER 331, DER661, DER 662), commercially available from the Dow Chemical Company,Midland, Mich.

Preferably the polymeric adhesive composition includes one or moreliquid epoxy resins and one or more solid epoxy resins.

The amount of the liquid epoxy resin may be sufficient so that the highglass transition temperature thermoplastic can be easily compounded inan extruder. For example, the weight ratio of the liquid epoxy resin tothe high glass transition temperature thermoplastic resin (e.g., apolysulfone according to the teachings herein) may be about 0.4 or more,about 0.7 or more, about 1.0 or more, about 1.3 or more, or about 1.6 ormore. If the amount of liquid epoxy resin is too high, the activatablematerial may be difficult to handle (e.g., the activatable material maybecome tacky or even flow at room temperature). The ratio of the liquidepoxy resin to the high glass transition temperature thermoplastic resinpreferably is about 7 or less, more preferably about 5 or less, and morepreferably about 4 or less. Preferably the liquid epoxy resin is presentin the activatable material in an amount of about 65 weight percent orless, more preferably about 60 weight percent or less, even morepreferably about 55 weight percent or less, and most preferably about 50weight percent or less, based on the total weight of the polymer in thecomposition (e.g., based on the total weight of the epoxy resin, thehigh temperature thermoplastic resin, and any core/shell polymer).Preferably the liquid epoxy resin includes or consists substantially of,or consists entirely of one or more multi-functional epoxy resins. Forexample, the liquid may include one or more epoxy phenol novolac resinsand/or one or more epoxy cresol novolac resins. Preferably the amount ofmulti-function liquid epoxy resin (e.g., having functionality of about2.1 or more, 2.3 or more, 2.5 or more, or 3.0 or more) is about 30weight percent or more, more preferably about 50 weight percent or more,even more preferably about 70 weight percent or more, and mostpreferably about 80 weight percent or more, based on the total weight ofthe one or more liquid epoxy resins. Preferably the liquid epoxy resinis present in the activatable material at a concentration of about 63weight percent or less, more preferably about 56 weight percent or less,even more preferably about 52 weight percent or less, and mostpreferably about 45 weight percent or less, based on the total weight ofthe activatable material. Preferably the liquid epoxy resin is presentin the activatable material at a concentration of about 5 weight percentor more, more preferably about 10 weight percent or more, even morepreferably about 20 weight percent or more, and most preferably about 26weight percent or more, based on the total weight of the activatablematerial.

The amount of the solid epoxy resin in the polymeric adhesivecomposition should be sufficient so that the composition is a solid atroom temperature. The solid epoxy resin also may contribute to the hightemperature performance of the composition after curing, as discussedherein. Preferably the solid epoxy resin is present at about 4 weightpercent or more, more preferably about 6 weight percent or more, evenmore preferably about 8 weight percent or more, and most preferablyabout 10 weight percent or more, based on the total weight of theactivatable material. The weight ratio of the solid epoxy resin to theliquid epoxy resin may be about 0.00 or more, about 0.05 or more, about0.10 or more, about 0.15 or more, about 0.2 or more, or about 0.25 ormore. The weight ratio of the solid epoxy resin to the liquid epoxyresin preferably is about 1.0 or less, about 0.8 or less, about 0.6 orless, or about 0.5 or less. The solid epoxy resin may include anychemical structure as described herein (e.g., homopolymer, copolymer,terpolymer, bisphenol-A, bisphenol-F, epoxy phenol novolac resin, epoxycresol novolac resin etc.). Preferably the solid epoxy resin includes,consists substantially of, or consists essentially of bisphenol-F epoxyresins. Solid epoxy resins may be characterized by molecular weight as atype 3, type 4, type 5, type 6, type 7, type 8, type 9, or type 10 epoxyresin. Preferred solid epoxy resins are type 4 or higher, morepreferably type 5 or higher, even more preferably type 6 or higher, andmost preferably type 7 or higher. Preferred solid epoxy resins are type10 or lower, more preferably type 9 or lower, and most preferably type 8or lower.

Impact Modifier

Generally, it is preferable for the polymeric adhesive composition toinclude at least one impact modifier. As used herein, like with anyother ingredients of the present invention, the term “impact modifier”can include one impact modifier or plural impact modifiers. Variousimpact modifiers may be employed in the practice of the presentinvention and often include one or more elastomers. It is generallypreferable for the impact modifier to be about 0.5 weight percent ormore, more preferably about 1 weight % or more, even more preferablyabout 1.5 weight percent or more, even more preferably about 2 weightpercent or more, even more preferably about 2.5 weight percent or more,and most preferably about 3.0 weight percent or more of the activatablematerial. The impact modifier preferably is present in an amount ofabout 20 weight % or less, more preferably about 16 weight percent orless, even more preferably about 15 weight percent or less, even morepreferably about 9% by weight or less, and most preferably about 7weight percent or less, based on the total weight of the activatablematerial. Higher or lower amounts may be used in particular embodiments.

In one embodiment of the present invention, the impact modifier includesat least one core/shell impact modifier and preferably the impactmodifier includes a substantial portion of core/shell impact modifier.In one preferred embodiment, the impact modifier is comprised of atleast 60%, more typically at least 80% and even more typically at least97% core/shell impact modifier. As used herein, the term core/shellimpact modifier denotes an impact modifier wherein a substantial portion(e.g., about 30 weight % or more, about 50 weight % or more, or about 70weight % or more) thereof is comprised of a first polymeric material(i.e., the first or core material) that is substantially entirelyencapsulated by a second polymeric material (i.e., the second or shellmaterial). The first and second polymeric materials, as used herein, canbe comprised of one, two, three or more polymers (or polymer blocks)that are combined and/or reacted together (e.g., sequentiallypolymerized) or may be part of separate or same core/shell systems.

The first and second polymeric materials of the core/shell impactmodifier can include elastomers, polymers, thermoplastics, copolymers,other components, combinations thereof or the like. In preferredembodiments, the first polymeric material, the second polymeric materialor both of the core/shell impact modifier include or are substantiallyentirely composed of (e.g., at least 70%, 80%, 90% or more by weight)one or more thermoplastics and/or one or more elastomers. The core/shellimpact modifier most preferably includes one or more thermoplastics andone or more elastomers. Exemplary thermoplastics include, withoutlimitation, styrenics, acrylonitriles, acrylates, acetates, polyamides,polyethylenes or the like.

The core/shell impact modifier may be prepared in an emulsion. Forexample, the core, the shell, or both may be prepared in an emulsion.After preparing the core/shell impact modifier, the core/shell impactmodifier may be removed from the emulsion. In one approach, a matrixfluid of the emulsion is replaced with a replacement fluids (such as apolymeric resin, a polymerizable monomer, or a polymerizableprepolymer). For example, some or all of the matrix fluid of theemulsion may be replaced with an epoxy resin (e.g., a liquid epoxyresin). The process may include a step of removing some or all of theoriginal matrix fluid. Preferably, agglomeration of the core/shellpolymer is avoided during the fluid exchange. The resulting core/shellimpact modifier in the replacement fluid preferably has a sufficientamount of the replacement fluid so that agglomeration is reduced,minimized, or entirely avoided. Preferably, some or all of thesurfactant (i.e., from the emulsion) may be removed during thereplacement of the matrix fluid with the replacement fluid. This may beparticularly beneficial when it is required to have improved adhesionand/or improved mechanical properties after heat aging, or afterhumidity aging, or after other environmental aging. The core/shellimpact modifiers may be formed by emulsion polymerization followed bycoagulation or spray drying. Here, it may be necessary to de-agglomeratethe core/shell impact modifier before, during, or after preparing thecomposition. The impact modifier preferably is formed of or at leastinclude a core/shell graft co-polymer. The first or core polymericmaterial of the graft copolymer preferably has a glass transitiontemperature substantially below (i.e., at least 10, 20, 40 or moredegrees centigrade) the glass transition temperature of the second orshell polymeric material. Moreover, it may be desirable for the glasstransition temperature of the first or core polymeric material to bebelow 23° C. while the glass temperature of the second or shellpolymeric material to be above 23° C., although not required.

Examples of useful core/shell graft copolymers are those whererelatively hard polymers or polymer blocks (e.g., polymers or polymerblocks including, consisting substantially of, or consisting entirely ofstyrene, acrylonitrile or methyl methacrylate) are grafted onto apolymeric core made from a relatively soft polymer (e.g., an elastomeror elastomeric containing polymer or polymer block such as butadiene orbutyl acrylate). The relative hardness of the polymers may be determinedby flexural modulus (e.g. as measured according to ASTM D790), forexample on the individual polymers or isolated polymer blocks. U.S. Pat.No. 3,985,703, which is herein incorporated by reference, describesuseful core/shell polymers, the cores of which are made from butylacrylate but can be based on ethyl isobutyl, 2-ethylhexel or other alkylacrylates or mixtures thereof. The core polymer, may also include othercopolymerizable compounds, such as compounds containing or consisting ofstyrene, vinyl acetate, methyl methacrylate, butadiene, isoprene,derivatives thereof, or any combination thereof. The core polymermaterial may also include a cross linking monomer having two or morenonconjugated double bonds of approximately equal reactivity such asethylene glycol diacrylate, butylene glycol dimethacrylate, and thelike. The core polymer material may also include a graft linking monomerhaving two or more nonconjugated double bonds of unequal reactivity suchas, for example, diallyl maleate and allyl methacrylate.

The shell portion may be polymerized from methyl methacrylate andoptionally other alkyl methacrylates, such as ethyl, butyl, or mixturesthereof methacrylates. Up to 40 percent by weight or more of the shellmonomers may be styrene, vinyl acetate, vinyl chloride, and the like.Additional core/shell graft copolymers useful in embodiments of thepresent invention are described in U.S. Pat. Nos. 3,984,497; 4,096,202;4,034,013; 3,944,631; 4,306,040; 4,495,324; 4,304,709; and 4,536,436,the entireties of which are herein incorporated by reference. Examplesof core/shell graft copolymers include, but are not limited to, “MBS”(methacrylate-butadiene-styrene) polymers, which are made bypolymerizing methyl methacrylate in the presence of polybutadiene or apolybutadiene copolymer rubber. The MBS graft copolymer resin generallyhas a styrene butadiene rubber core and a shell of acrylic polymer orcopolymer. Examples of other useful core/shell graft copolymer resinsinclude, ABS (acrylonitrile-butadiene-styrene), MABS(methacrylate-acrylonitrile-butadiene-styrene), ASA(acrylate-styrene-acrylonitrile), all acrylics, SA EPDM(styrene-acrylonitrile grafted onto elastomeric backbones ofethylene-propylene diene monomer), MAS (methacrylic-acrylic rubberstyrene), and the like and mixtures thereof.

The impact modifier preferably is provided as core/shell particles. In acore/shell particle (e.g., having an elastomeric core), theconcentration of the impact modifier typically refers to the amount ofthe core portion. The impact modifier preferably is provided as aparticle dispersion including the core/shell particles dispersed in amatrix material and most preferably a carrier liquid Preferred matrixmaterials have a melting temperature of about 90° C. or less and morepreferably about 60° C. or less, and preferred carrier liquids have amelting temperature of about 20° C. or less, about 10° C. or less, orabout 5° C. or less. Preferably, the carrier liquid is a liquid epoxyresin, such as a liquid epoxy resin having properties and/or structureas described herein. The amount of the matrix material (e.g., thecarrier liquid) preferably is about 25 weight percent or more, morepreferably about 50 weight percent or more, and most preferably about 60weight percent or more, based on the total weight of the dispersion(i.e., including the matrix material and the particles). The amount ofthe matrix material (e.g., the carrier liquid) preferably is about 95weight percent or less (although higher amounts may be employed), morepreferably about 90 weight percent or less, and most preferably about 85weight percent or less, based on the total weight of the dispersion.Preferably, the carrier liquid includes, consists substantially of, orconsists entirely of a liquid novolac resin, a liquid bisphenol-A epoxyresin, a liquid bisphenol-F epoxy resin, or any combination thereof. Thedispersion particles preferably have a diameter of about 25 nm or more,more preferably about 50 nm or more, even more preferably about 75 nm ormore, and most preferably about 100 nm or more. The dispersion particlespreferably have a diameter of about 10 μm or less, more preferably about2 μm or less, even more preferably about 900 nm or less, even morepreferably about 600 nm or less, and most preferably about 400 nm orless.

Examples of useful impact modifiers include, but are not limited tothose sold under the tradename, Kane ACE™, commercially available fromKaneka Corporation (Japan), and PARALOID, commercially available fromRohm & Haas Co. One particularly preferred grade of PARALOID impactmodifier is polymethyl methacrylate shell and MBS core modifier soldunder the designation EXL-2691A. One particularly preferred grade ofKane ACE impact modifier is a core/shell dispersion including about 37weight percent core/shell particles having a polybutadiene rubber coredispersed in a liquid bisphenol-F carrier liquid. This grade hascore/shell particles including about 80 to about 90 weight percent coreand about 10 to about 20 weight percent shell.

While it is contemplated that various polymer/elastomer adducts may beemployed according to the present invention, one preferred adduct is anepoxy/elastomer adduct. Preferably, an elastomer-containing adduct isemployed in the activatable material of the present invention. Theepoxy/elastomer hybrid or adduct may be included in an amount of up toabout 30% by weight of the activatable material. If present, the adduct(e.g., the elastomer-containing adduct) preferably is approximatelyabout 0.1 weight percent or more of the activatable material. The adduct(e.g., the elastomer-containing adduct) preferably is approximately 20weight percent or less, more preferably about 10 weight percent or less,and most preferably about 4 weight percent or less of the activatablematerial. Of course, the elastomer-containing adduct may be acombination of two or more particular adducts and the adducts may besolid adducts or liquid adducts at a temperature of 23° C. or may alsobe combinations thereof. In one preferred embodiment, the activatablecomposition is substantially or entire free of a polymer/elastomeradduct.

The activatable material may optionally include one or more additionalpolymers (e.g., homopolymers or copolymers), which can include a varietyof different polymers, such as thermoplastics, elastomers, plastomerscombinations thereof or the like. For example, and without limitation,polymers that might be appropriately incorporated into the polymericadmixture include halogenated polymers, polycarbonates, polyketones,urethanes, polyesters, silanes, allyls, olefins, styrenes, acrylates,methacrylates, epoxies, silicones, phenolics, rubbers, polyphenyleneoxides, terephthalates, acetates (e.g., EVA), acrylates, methacrylates(e.g., ethylene methyl acrylate polymer) or mixtures thereof. Otherpotential polymeric materials may be or may include, without limitation,polyolefin (e.g., polyethylene, polypropylene) polystyrene,polyacrylate, poly(ethylene oxide), poly(ethyleneimine), polyester,polyurethane, polysiloxane, polyether, polyphosphazine, polyamide,polyimide, polyisobutylene, polyacrylonitrile, poly(vinyl chloride),poly(methyl methacrylate), poly(vinyl acetate), poly(vinylidenechloride), polytetrafluoroethylene, polyisoprene, polyacrylamide,polyacrylic acid, polymethacrylate. If employed, any such additionalpolymers or copolymers preferably are present (in total) at aconcentration of about 10 weight percent or less, based on the totalweight of the polymer in the composition, and preferably at aconcentration of about 5 weight percent or less (more preferably about1.5 weight percent or less, and most preferably about 0.5 weight percentor less) based on the total weight of the activatable material. Ifpresent, the one or more additional polymers (each or in total) may beabout 0.1 weight percent or more of the weight of the activatablecomposition.

The thermoplastic polyethers typically include pendant hydroxylmoieties. The thermoplastic polyethers may also include aromaticether/amine repeating units in their backbones. The thermoplasticpolyethers of the present invention preferably have a melt index betweenabout 5 and about 100, more preferably between about 25 and about 75 andeven more preferably between about 40 and about 60 grams per 10 minutesmeasured using 2.16 kg mass at a temperature of about 190° C. Of course,the thermoplastic polyethers may have higher or lower melt indicesdepending upon their intended application. Preferred thermoplasticpolyethers include, without limitation, polyetheramines, poly(aminoethers), copolymers of monoethanolamine and diglycidyl ether,combinations thereof or the like. The thermoplastic polyether preferablyhas a glass transition temperature of about 180° C. or less, about 140°C. or less, or about 100° C. or less. The thermoplastic polyetherpreferably has a glass transition temperature of about 30° C. or more,about 40° C. or more, or about 50° C. The glass transition temperaturemay be measured by dynamic mechanical analysis (see e.g., ISO6721-11:2012).

Preferably, the thermoplastic polyethers are formed by reacting an aminewith an average functionality of 2 or less (e.g., a difunctional amine)with a glycidyl ether (e.g., a diglycidyl ether). As used herein, theterm difunctional amine refers to an amine with an average of tworeactive groups (e.g., reactive hydrogens).

According to one embodiment, the thermoplastic polyether is formed byreacting a primary amine, a bis(secondary) diamine, a cyclic diamine, acombination thereof or the like (e.g., monoethanolamine) with adiglycidyl ether or by reacting an amine with an epoxy-functionalizedpoly(alkylene oxide) to form a poly(amino ether). According to anotherembodiment, the thermoplastic polyether is prepared by reacting adifunctional amine with a diglycidyl ether or diepoxy-functionalizedpoly(alkylene oxide) under conditions sufficient to cause the aminemoieties to react with the epoxy moieties to form a polymer backbonehaving amine linkages, ether linkages and pendant hydroxyl moieties.Optionally, the polymer may be treated with a monofunctional nucleophilewhich may or may not be a primary or secondary amine. Additionally, itis contemplated that amines (e.g., cyclic amines) with one reactivegroup (e.g., one reactive hydrogen) may be employed for forming thethermoplastic polyether. Advantageously, such amines may assist incontrolling the molecular weight of the thermoplastic ether formed.Examples of preferred thermoplastic polyethers and their methods offormation are disclosed in U.S. Pat. Nos. 5,275,853; 5,464,924 and5,962,093, which are incorporated herein by reference for all purposes.Advantageously, the thermoplastic polyethers can provide the activatablematerial with various desirable characteristics such as desirablephysical and chemical properties for a wide variety of applications asis further described herein.

Blowing Agent

One or more blowing agents may be added to the activatable material forproducing inert gasses that form, as desired, an open and/or closedcellular structure within the activatable material and/or for adheringtwo substrates that are separated by a gap (e.g., by compensating forgap variations). In this manner, it may be possible to lower the densityof articles fabricated from the material. In addition, the materialexpansion can help to improve adhesion capability.

The blowing agent may include one or more nitrogen containing groupssuch as amides, amines and the like. Examples of suitable blowing agentsinclude azodicarbonamide, dinitrosopentamethylenetetramine,4,4_(i)-oxy-bis-(benzenesulphonylhydrazide), trihydrazinotriazine andN,N_(i)-dimethyl-N,N_(i)-dinitrosoterephthalamide.

An accelerator for the blowing agents may also be provided in theactivatable material. Various accelerators may be used to increase therate at which the blowing agents forms gasses (e.g., inert gasses)and/or decrease the temperature at which the blowing agent forms thegasses. One preferred blowing agent accelerator is a metal salt, or isan oxide, e.g. a metal oxide, such as zinc oxide. Other preferredaccelerators include modified and unmodified thiazoles or imidazoles.

Amounts of blowing agents and blowing agent accelerators can vary widelywithin the activatable material depending upon the type of cellularstructure desired, the desired amount of expansion of the activatablematerial, the desired rate of expansion and the like. If employed,exemplary ranges for the amounts of blowing agents and blowing agentaccelerators in the activatable material range from about 0.001% byweight to about 7% by weight and may even be in the activatable materialin fractions of weight percentages. For example, the amount of theblowing agent may be about 7 weight percent or less, about 4 weightpercent, about 3 weight percent or less, or about 2 weight percent orless, based on the total weight of the activatable material. If employedin the activatable material, the blowing agent is preferably present inan amount of about 0.001 weight percent or more, more preferably about0.01 weight percent or more, even more preferably about 0.1 weightpercent or more, and most preferably about 0.4 weight percent or more,based on the total weight of the activatable material.

Curing Agent

One or more curing agents and/or curing agent accelerators may be addedto the activatable material. Amounts of curing agents and curing agentaccelerators can, like the blowing agents, vary widely within theactivatable material depending upon the type of cellular structuredesired, the desired amount of expansion of the activatable material,the desired rate of expansion, the structure (e.g., molecular weight,chemical structure, and functionality) of the epoxy resins, the desiredstructural properties of the activatable material and the like.Exemplary ranges for the curing agents or curing agent acceleratorspresent in the activatable material range from about 0.001% by weight toabout 20% by weight. For example, the curing agent, the curing agentaccelerators, or the total of the curing agent and the curing agentaccelerators may be present in an amount of i) about 0.01 weight % ormore, about 0.1 weight percent or more, about 0.4 weight percent ormore, about 0.8 weight percent or more, about 1.4 weight percent ormore, or about 2.0 weight percent or more and/or ii) about 18 weightpercent or less, about 15 weight percent or less, about 12 weightpercent or less, or about 9 weight percent or less, based on the totalweight of the activatable material.

Preferably, the curing agents assist the activatable material in curingby crosslinking of the polymers, epoxy resins or both. It is alsopreferable for the curing agents to assist in thermosetting theactivatable material. Useful classes of curing agents are materialsselected from aliphatic or aromatic amines or their respective adducts,amidoamines, polyamides, cycloaliphatic amines, anhydrides,polycarboxylic polyesters, isocyanates, or mixtures thereof. Particularpreferred curing agents include modified and unmodified polyamines orpolyamides such as triethylenetetramine, diethylenetriaminetetraethylenepentamine, cyanoguanidine, dicyandiamides and the like. Anaccelerator for the curing agents (e.g., a modified or unmodified ureasuch as methylene diphenyl bis urea, an imidazole or a combinationthereof) may also be provided for preparing the activatable material.

The present invention contemplates the omission of a blowing agent and acuring agent. Preferably, however, the curing agent, the blowing agentor both are present in the activatable material and thermally activated.Alternatively, other agents may be employed for realizing activation byother means, such as moisture, radiation, or otherwise.

Filler

The activatable material may also include one or more fillers, includingbut not limited to particulated materials (e.g., powder), beads,microspheres, or the like. Preferably the filler includes a materialthat is generally non-reactive with the other components present in theactivatable material. While the fillers may generally be present withinthe activatable material to take up space at a relatively low weightand/or a relatively low cost, it is contemplated that the fillers mayalso impart one or more properties (e.g., leveling, strength, or impactresistance) to the activatable material.

Examples of fillers include silica, diatomaceous earth, glass, clay(e.g., including nanoclay), talc, pigments, colorants, glass beads orbubbles, glass, carbon or ceramic fibers, polymeric fibers such as nylonor polyaramid fibers (e.g., KEVLAR® fibers), and the like. Such fillers,particularly clays, may assist the activatable material in levelingitself during flow of the material. The clays that may be used asfillers may include clays from the kaolinite, illite, chloritem,smecitite or sepiolite groups, which may be calcined. Examples ofsuitable fillers include, without limitation, talc, vermiculite,pyrophyllite, sauconite, saponite, nontronite, montmorillonite ormixtures thereof. The clays may also include minor amounts of otheringredients such as carbonates, feldspars, micas and quartz. The fillersmay also include ammonium chlorides such as dimethyl ammonium chlorideand dimethyl benzyl ammonium chloride. Titanium dioxide might also beemployed.

In one preferred embodiment, one or more mineral or stone type fillerssuch as calcium carbonate, sodium carbonate or the like may be used asfillers. In another preferred embodiment, silicate minerals such as micamay be used as fillers.

When employed, the fillers in the activatable material may be present inan amount of about 0.1 weight percent or more, about 5 weight percent ormore, about 20 weight percent or more, or about 30 weight percent ormore, based on the total weigh of the activatable material. Preferably,the filler is present in an amount of about 70 weight percent or less,more preferably about 55 weight percent or less, even more preferablyabout 50 weight percent or less, even more preferably about 40 weightpercent or less, and most preferably about 25 weight percent or less,based on the total weight of the activatable material. For example, thefiller may be present in a range from 5 weight % to 60 weight % of theactivatable material, or from about 10 to 55% by weight of theactivatable material. It will be appreciated that the activatablematerial may be substantially free of clay and/or other phyllosilicates.For example, the activatable material may include from about 0% to about3% by weight, and more preferably less than 1% by weight of clay and/orother phyllosilicates. The filler may be present as powder particles.Such powder particles preferably have a mean particle diameter of about0.01 μm or more, more preferably about 0.1 μm or more, and mostpreferably about 1 μm or more. The powder particles preferably have amean particle diameter of about 80 μm or less, more preferably about 50μm or less, even more preferably about 25 μm or less, and mostpreferably about 15 μm or less. The amount of the powdered mineral typefiller in the activatable material preferably is from about 1% to about40% by weight, more preferably from about 5% to about 25% by weight,based on the total weight of the activatable material.

Rheology Modifier

The activatable composition preferably includes a rheology modifier. Therheology modifier preferably is a filler material. The rheology modifiermay be an organic or an inorganic material. The rheology modifierpreferably remains a solid at typical use temperatures and preferablyremains a solid at typical processing temperatures. Preferably, therheology modifier is a solid at a temperature of about 150° C., morepreferably at a temperature of about 175° C., even more preferably about200° C., and most preferably about 225° C. The rheology modifierpreferably is a plate shaped or fiber shaped material having an aspectratio (i.e., a ratio of the longest dimension to the shortest dimension,such as the length to diameter ratio of fibers) of about 3 or more,preferably about 5 or more, more preferably about 10 or more, and mostpreferably about 20 or more. An organic rheology modifier may include,consist essentially of, or consist entirely of polymeric fibers.Particularly preferred polymeric fibers include polyaramid fibers (e.g.,para-aramid fibers, such as KEVLAR® fibers). Preferred fibers for therheology modifier have an average length of about 50 mm or less (e.g.,about 35 mm or less).

The viscosity modifier preferably increases the zero shear viscosity ofthe composition (measured at about 100° C.) by about 10% or more, morepreferably about 40% or more, and most preferably about 100% or more.For example, such increases in the viscosity may be obtained with about3% of the viscosity modifier, about 2% of the viscosity modifier, about1% of the viscosity modifier, or even less than 1% of the viscositymodifier.

The composition may include one or more additives. Preferred additivesinclude antioxidants, heat stabilizers, process aids, flame retardants,and other stabilizers.

Compounding

The polymeric adhesive compositions (i.e., the activatable compositions)according to the teachings may be compounded using any method employedin the compounding of polymers. The ingredients may be compoundedtogether in a single step or in a plurality of steps (such as byemploying intermediate steps to compound together at least a portion ofthe ingredients). A compounding step may employ a batch mixer and/or acontinuous mixer. Examples of continuous mixers that may be employedinclude extruders and kneaders, such as a single screw extruder and atwin screw extruder. Any step of compounding may employ application ofshear, application of heat, cooling, or any combination thereof. Forexample, heat may be added in a first stage of compounding (e.g., tomelt or soften a polymer) and cooling may be applied at a second laterstage (e.g., to reduce or prevent premature reaction of an ingredient).The compounding of the activatable compositions preferably is performedat a temperature sufficiently low so that curing of the epoxy resin issubstantially avoided. The compounding of the activatable compositionspreferably is performed at conditions (e.g., sufficiently lowtemperature and/or sufficiently low shear rate) such that the particlesize of the core/shell polymer is substantially maintained. Thecompounding of the activatable composition preferably is performed usingsufficient shear so that some or all of the agglomerated core/shellparticles are de-agglomerated during the processing. This may beparticularly advantageous when employing dry core/shell particles.

In preparing an activatable material according to the teachings herein,it is contemplated that an intermediate compounding step may be employedthat includes compounding the high glass transition temperaturethermoplastic polymer with at least a portion of the liquid epoxy resinprior to compounding the high glass transition temperature thermoplasticpolymer with one or more other ingredients (e.g., an impact modifier, afiller, a curative, a blowing agent, a solid epoxy resin, or anycombination thereof). Such an intermediate compound preferably includesthe high glass transition temperature thermoplastic polymer in an amountof about 5 weight percent or more of, more preferably about 15 weightpercent or more, even more preferably about 25 weight percent or more,and most preferably about 35 weight percent or more. For example, theintermediate compound may be a blend including, consisting substantiallyof, or consisting entirely of about 30 to about 80 weight percent liquidepoxy resin and about 20 to about 70 weight percent of the high glasstransition temperature thermoplastic polymer. The process may include astep of compounding the intermediate compound with one or moreadditional ingredients (e.g., an impact modifier, a filler, a curative,a blowing agent, a solid epoxy resin, additional liquid epoxy resin, orany combination thereof). The fully compounded polymeric adhesivecomposition preferably is a multiphase material including one or morefiller phases and a continuous polymer phase. The continuous polymerphase may also comprise multiple phases including a first polymer phaseincluding the impact modifier and a second polymer phase including thehigh glass transition thermoplastic polymer. The epoxy resin may bepresent in the first or second polymer phase. Preferably some or all ofthe epoxy resin is present in a third polymer phase.

The polymeric adhesive composition is an activatable material and mayneed to be stored under conditions that minimizes or reduces reactionsduring storage. For example, the polymeric adhesive composition may bestored at temperature of about 80° C. or less, preferably about 60° C.or less, even more preferably about 45° C. or less, and most preferablyabout 40° C. or less.

The polymeric adhesive composition is a solid material and may be storedas slabs, as shaped parts (e.g., preform parts, or otherwise), aspellets, and the like. The polymeric adhesive composition may have ashape and/or size suitable for feeding into a screw and barrel assembly,such as for an extrusion machine, an injection molding machine, or ablow molding machine. For example, the polymeric adhesive compositionmay be in the form of pellets or other particles having a mass of about1 g or less and/or having a mass of about 0.01 g or more. The polymericadhesive composition may have a shape and/or size suitable for applyingto a surface using a spraying device, such as electrospray, a compressedgas spray gun, or other spraying device having a spray nozzle. Forexample, the polymeric adhesive composition may be in the form of smallparticles (e.g., having a mass of about 0.05 g or less, about 0.01 g orless, or about 0.001 g or less). The polymeric adhesive composition maybe in the form of microparticles. It will be appreciated that particleshaving a high surface to volume ratio may have a generally higherpropensity to agglomerate than larger particles. Preferably, thecomposition is free of pellet blocking and powder agglomeration. Theratio of the solid epoxy component(s) to the liquid epoxy component(s)preferably is sufficiently high so that the particles of the polymericadhesive composition are free flowing and agglomeration is avoided priorto being applied to a surface.

The polymeric adhesive composition may be shaped into a part or acomponent using any shaping process employed in the shaping of polymericmaterials. For example, the polymeric adhesive composition may be shapedusing an injection molding machine, using an extruder (e.g., extrudingthrough one or more dies, such as to achieve a desired profile shape),using a compression molding machine, using a mill, using a cuttingdevice, using a thermoforming device, using a robotic extrusion device,and the like. The step of shaping the polymeric adhesive composition mayemploy shear and heat. The polymeric adhesive composition may beextruded or molded directly onto a substrate to which it will beadhered. The polymeric adhesive composition may be shaped into a partfor adhering to a substrate at a later stage. It will be appreciatedthat the polymeric adhesive composition may be used in an applicationthat adheres two or more substrates or components. The polymericmaterial may be extruded or molded directly onto both of the componentsto be adhered. The polymeric material may be extruded or molded directlyonto one of the components to be adhered and attached to the secondcomponent at a later time. The polymeric material may be shaped withoutcontacting the components to be adhered and may only contact thecomponents at one or more later times.

Although the activatable material may adhere to the substrates and/orcomponents, the material requires curing and/or activation of theblowing agent to increase the adhesion. The curing may be performed atone or more temperatures of about 140° C. or more, for a total time ofabout 5 minutes or more. For example, the curing temperature preferablyis about 150° C. or more, more preferably about 160° C. or more, andmost preferably about 170° C. or more. The curing time preferably isabout 10 minutes or more, more preferably about 20 minutes or more, andmost preferably about 25 minutes or more. The curing temperature ispreferably about 275° C. or less, and more preferably about 225° C. orless. The curing time is preferably about 12 hours or less, morepreferably about 2 hours or less, and most preferably about 1 hour orless.

Applications

The activatable materials according to the teachings herein may beemployed in applications required adhesion at elevated temperatures(such as elevated working temperatures). For example, after activation(e.g., crosslinking and/or expansion) may provide adhesion at elevatedtemperatures of about 100° C. or more, about 120° C. or more, about 140°C. or more, or about 180° C. As such, the materials may be employed inunder the hood applications in a vehicle having an internal combustionengine. For example, the materials may be employed in a hybrid vehiclehaving an electric motor and an internal combustion engine. Such hybridvehicles may beneficially employ the activatable materials for adheringone or more components that is exposed to a operating temperatures ofabout 160° C. or less (preferably about 140° C. or less) and/or peaktemperature excursions of about 200° C. or less (preferably about 180°C. or less). For example, the activatable material may be employed foradhering components exposed to an operating temperature of about 100° C.or more (or about 110° C. or more, or about 120° C. or more) and/or apeak temperature of about 140° C. or more (or about 160° C. or more, orabout 170° C. or more).

Device

A polymeric adhesive component including a high glass transitiontemperature thermoplastic resin according to the teachings herein may beemployed in a device for adhering two or more components of the device.For example, the device may include a first component attached to one ormore second components by a polymeric adhesive component. The polymericadhesive component may be formed from a polymeric adhesive composition,such as a polymeric adhesive composition according to the teachingsherein. Typically, the polymeric adhesive composition is cross-linked orotherwise reacted and/or expanded (e.g., using one or more blowingagents) in forming the polymeric adhesive component. The secondcomponents may be attached to a surface of the first component that isflat or curved. Preferably, the second components are attached to asurface of the first component that is curved. For example, the firstcomponent may have a surface that is cylindrical ring in shape (or aportion or section of a cylindrical ring). More preferably the secondcomponents are attached to a concave surface of the first component. Thefirst component may have an axis of rotation and a length that extendsin the direction of the axis of rotation.

The first component may be a metal, a polymer, a ceramic, or anycombination thereof. Preferably the first component consistssubstantially of or entirely of a metal material.

The second component may be a metal, a polymer, a ceramic, or anycombination thereof. Preferably the second component consistssubstantially of or entirely of a metal material. The first component orthe second component may be formed of the same material or fromdifferent materials. The second components may have a length. Preferablythe second component is arranged so that the length of the secondcomponent is parallel with the axis of rotation of the first component.The second component may have a width. Preferably the width of thesecond component is aligned with a tangential direction of a curvedsurface of the first component. The second component may have athickness. Preferably the thickness of the second component extends fromthe polymeric adhesive towards the axis of rotation of the firstcomponent, and/or in a direction parallel to the normal direction of thecurved surface of the first component (e.g. in a radial direction). Oneor more (e.g., each) of the second components may have a lateral surfacethat is in contact with or attached to a lateral surface of an adjacentsecond component. For example, a second component may have opposingfirst and second lateral surfaces where the first lateral surface is incontact with or attached to a lateral surface of a first adjacent secondcomponent, and the second lateral surface is in contact with or attachedto a lateral surface of a second adjacent second component. The secondcomponent may be described as teeth that protrude from the firstcomponent. Two adjacent second components preferably nest or interlockwith each other. As such, the lateral surfaces may include features suchas one or more grooves and/or one or more ridges that allow for suchnesting and/or interlocking. It will be appreciated that the lateralsurface may instead be generally flat surfaces. The device may include asufficient number of second components (e.g., teeth) so that the secondcomponents substantially or entirely cover a circumference (e.g., acircumference of a concave surface) of the first component. By way ofexample, the first substrate may include or consist of a ring having anaxis and some or all of a circumference (e.g., an inner circumference oran outer circumference) of the ring may be covered by the teeth. Theteeth may have a length aligned with the axis of the ring. The polymericadhesive component may be used for attaching the teeth in a stator ring.The teeth may form a magnetic field or include a wire winding. Such astator ring containing device may be particularly suitable for a motor,such as a hybrid motor in a vehicle.

The polymeric adhesive component may have a uniform thickness (e.g.,between the first component and the second component) or may have athickness that varies. The thickness of the polymeric adhesive componentmay be sufficient so that the polymeric adhesive component can providemechanical durability to the device. Preferably, the polymeric adhesivecomponent has a thickness of about 0.1 mm or more, more preferably about0.4 mm or more, and most preferably about 0.6 mm or more. The polymericadhesive component preferably has a thickness of about 10 mm or less,more preferably about 5 mm or less, even more preferably about 2.5 mm orless, and most preferably about 1.8 mm or less. The polymeric adhesivecomponent may be expanded (e.g., so that it has open cells and/or closedcells) or may be substantially free of expansion. The level of expansionis the ratio of the increase in volume to the initial volume of thepolymeric adhesive composition prior to expansion, expressed as apercentage:

V.E.=100%×(V _(expanded) −V _(initial))/V _(initial).

The level of expansion of the polymeric adhesive component may be about0% or more, about 10% or more, about 20% or more, or about 40% or more.The level of expansion of the polymeric adhesive component preferably isabout 400% or less, more preferably about 220% or less, even morepreferably about 130% or less, and most preferably about 70% or less.

The first component and second component(s) may be attached by arrangingthe polymeric adhesive composition between the first and secondcomponents and then heating the materials for curing and/or expandingthe polymeric adhesive composition so that the polymeric adhesivecomponent is formed. The polymeric adhesive composition may be suppliedas a separate component, such as a pre-cured component that is molded,extruded or otherwise shaped, or may be attached to the first or secondcomponents prior to heating (e.g., prior to curing and/or expanding).The heating may include heating to a temperature of about 100° C. ormore, about 140° C. or more, about 150° C. or more, or about 170° C. Theheating may be for a sufficient time so that the composition expandsand/or cures. The heating temperature should be sufficiently low so thatany degradation of the polymeric adhesive composition is reduced,minimized, or eliminated. Preferably the heating temperature is about320° C. or less, more preferably about 260° C. or less, even morepreferably about 210° C. or less, and most preferably about 190° C. orless.

The devices according to the teachings herein may be particularly usefulfor applications having generally high operating temperatures, such asan operating temperature of about 130° C. or more, about 150° C. ormore, about 163° C. or more, or about 170° C. The operating temperaturepreferably is about 280° C. or less, more preferably about 220° C. orless, and most preferably about 200° C. or less.

It will be appreciated that useful devices may include one or moreadditional components in addition to the first component, the secondcomponent(s), and a component formed from the polymeric adhesivecomposition. For example, the device may include one or more componentsincluding windings for carrying an electric current and/or one or morecomponents axially aligned with the rotational axis of the cylinder(e.g., having a rotational axis that is identical to the rotational axisof the cylinder) of the first substrate (e.g., for rotating about therotational axis or for supporting a component that rotates).

FIG. 3 illustrates features of a device 10 including a first component(i.e., a first substrate) 12 attached to a second component (i.e., asecond substrate) 16, by a polymeric adhesive 14. With reference to FIG.3, the polymeric adhesive 14 may cover the space between the firstcomponent 12 and the second component 16 and/or may directly attach thefirst component 12 and the second component 16. FIG. 4 illustratesfeatures of a device 10′ having two or more second components 16, 16′,each attached to the first component 12. As illustrated in FIG. 5, asecond component 16 may be in contacted with and/or attached to anothersecond component 16′ along a lateral surface 18. As illustrated in FIG.6, the device 20 may include a plurality of second components 22, 22′,22″ that nest. For example, a second components may have a lateralsurface 28 that mates with a lateral surface of an adjacent secondcomponent.

With reference to FIG. 7-9, the first component 32, may have a curvedsurface 38. For example, the first component 32, may have a cylindricalring shape. As such, the first component may have an axis of rotation(e.g., the axis of the cylinder). The second components 36 may beattached to the first component 32 by a layer of the polymeric adhesive34 that substantially or entirely covers a circumference of the surface38 of the first component 32. Adjacent second components may be incontact or directly attached (e.g., as shown in FIG. 7 and FIG. 8) ormay be spaced apart (e.g., as shown in FIG. 9).

Test Method

Volume expansion is calculated by first measuring the initial volume (atabout 25° C.) of a 23 mm×25 mm×1 mm specimen of the polymeric adhesivecomposition, curing the composition at 175° C. for 30 minutes, and thenmeasuring the volume after the cured material has cooled to about 23° C.The volume expansion is the ratio of the increase in volume to theinitial volume.

Unless otherwise stated, density measurements are taken at 23° C.

Lap shear test is performed on a tensile test device at a cross-headspeed of 10 mm/min. All specimens are cured at 175° C. for 30 minutesand then cooled to room temperature prior to testing. The initial samplesize is 25×25×1 mm, such as illustrated in FIGS. 1A, and 2. Formaterials that include a blowing agent the amount of blowing agent isselected to result in a volume expansion of 150 to 350 percent (seee.g., FIG. 1A before expansion and FIG. 1B after expansion of thepolymeric adhesive composition 6 and 6′). When testing the materialsincluding a blowing agent, a bond line thickness of 2 mm is used (FIGS.1A and 1B). When testing the material without a blowing agent (or withminimal expansion) 8, a bond line thickness equal to the thickness ofthe uncured specimen is used (i.e., 1 mm), such as illustrated in FIG.2. With reference to FIGS. 1A, 1B, and 2, the lap shear testing isperformed on substrates 4, preferably of 1.8 mm thick hot dippedgalvanneal which are free of oil. The maximum stress in MPa is measured.The lap shear is tested at a cross-head rate of 10 mm/min with adistance of about 112.5 mm between the grips.

The type of failure is characterized (according to PSA Peugeot Citroen,Méthode d′essai matériaux, D41 1108, ADHESIFS RESISTANCE ENTRACTION-CISAILLEMENT (METHODE DES CALES), Jun. 10, 2008, incorporatedherein by reference in its entirety) and recorded. Unless otherwisestated, the failure mode is characterized as 100% superficial cohesivefailure, which is considered cohesive failure.

Unless otherwise specified the hot dipped galvanneal is HDGHX420LAD+Z100MBO and is cleaned with acetone and dried prior topreparing the specimens.

Lap shear testing is done at various temperatures (e.g., at 23° C., 90°C., 120° C., 150° C., 180° C., and 210° C.) on specimens cured at a 175°C. for 30 minutes.

Tensile testing is measured according to ISO 527, using a specimen typeJISK 6301-1-MET, having a dogbone shape with a total length of about 120mm, a width in the wide tab sections of about 25 mm, and a width in thenarrow test regions of about 10 mm. The test speed (cross-head rate) isabout 10 mm/min, the distance between the grips is about 75 mm, and theextensometer distance is about 35 mm. Tensile properties are measured atabout 23° C. on uncured specimens and under controlled temperatureconditions of 23° C., 120° C., 150° C., 180° C., or 210° C. on curedspecimens (cured at 175° C. for 30 minutes).

EXAMPLES

Ingredients

OMICURE™ 52M is an aromatic substituted urea commercially available fromEMERALD PERFORMANCE MATERIALS LLC, Moorestown, N.J., including 95-100weight percent methylene diphenyl bis(dimethyl urea).

Epoxy A: ARALDITE® 6097 is a solid unmodified bisphenol-A based epoxyresin (type 7) having a softening point of about 125-135° C., an epoxideequivalent weight of about 1,695-1,885 (as measured according to ISO3001), a density of about 1.20 g/cm³ (measured at 25° C.), a viscosityof about 1800-2600 mPa s (Falling ball method measured according to ISO12058-1 at 25° C., 40% in butylcarbitol), a Mettler softening point ofabout 121-132° C. (measured according to DIN 51920), and a hydroxylcontent of about 3.2 eq/kg (measured according to ISO/DIS 4629), and iscommercially available from HUNTSMAN ADVANCED MATERIALS AMERICAS, TheWoodlands, Tex.

Epoxy B: ARALDITE® ECN 9699 is an epoxy cresol novolac resin having andfunctionality of about 5.5., a viscosity of about 7,000-10,000 mPa s(measured at 130° C.), an epoxy equivalent weight of 205-225g/equivalent, and a Mettler softening point of about 80-100° C., and iscommercially available from HUNTSMAN ADVANCED MATERIALS AMERICAS, TheWoodlands, Tex.

Epoxy C1—ARALDITE® EPN 9850 is an epoxy phenol novolac resin having anepoxy equivalent weight of about 168-178, a density of about 1.2 g/cm³at 25° C., and a viscosity of about 20,000-26,000 cP at 25° C.

Epoxy C2—EPALLOY® 8250 is an epoxy phenol novolac resin having an epoxyequivalent weight of about 165-178, a viscosity of about 18,000-28,000cps at 25° C., a functionality of about 2.65, and a residualepichlorohydrin concentration of about 10 ppm, and is commerciallyavailable from EMERALD PERFORMANCE MATERIALS LLC, Moorestown, N.J.

Kane Ace 267 is a core/shell polymeric particles having a core of apoly(butadiene) rubber dispersion (about 37% weight percent) and EPON®863 liquid bisphenol F (about 63 weight percent) and is commerciallyavailable from Kaneka Tex. Corporation (Pasedena, Tex.). The particleshave a diameter of about 100 nm to about 300 nm.

Epoxy D: ARALDITE® GY282 is a liquid bisphenol F epoxy resin having anepoxy equivalent weight of about 171.

GENITRON® LE is an Azodicarbonic acid diamide preparation having anaverage particle size of about 3.1-4.5 microns, and a concentration ofazodicarbonic acid diamide of about 57-63 weight percent, and iscommercially available from LANXESS US (Pittsburgh, Pa.).

Masterbatch A is a masterbatch including about 20 weight percent KEVLAR®brand aramid fiber pulp and about 80 weight percent bisphenol-A solidepoxy resin.

Dyhard 100S—Is a micronized dicyandiamide curing agent.

UDELL® P1700 is a thermoplastic polysulfone having a melt flow rate ofabout 6.5 g/10 min as measured according to ASTMD D1238 at 343° C./2.16kg, a specific gravity of about 1.24 as measured according to ASTM D792,a tensile modulus of about 2480 MPa as measured according to ASTM D638,an elongation at break of about 50-100% as measured according to ASTMD638, a flexural modulus of about 2690 MPa as measured according to ASTMD790, a heat distortion temperature of about 174° C. as measuredaccording to ASTM D648 under a load of 1.8 MPa, unannealed, a glasstransition temperature of about 185° C. to about 215° C., and a notchedIzod impact strength of about 69 J/m as measured according to ASTM D256,and is commercially available from SOLVAY.

Example 1

Example 1 is prepared by mixing UDELL® P1700 thermoplastic polysulfonewith a portion of epoxy C at a weight ratio of about 1:1 to form anepoxy/sulfone blend. The epoxy/sulfone blend is then compounded withepoxy A, epoxy B, pigment, additional epoxy C1, Core/shell polymer A,Masterbatch A, Calibrite OG, zinc oxide, Dyhard 100S, Omicure 52M, andGenitron LE, in the proportions shown in Table 1. The compoundingtemperature was maintained below 100° C. The density and tensileproperties of the activatable composition are measured at about 23° C.Cured tensile specimen are prepared by curing the material at 175° C.for 30 minutes. The tensile properties of the cured material aremeasured at about 23° C. and at about 150° C. The volume expansion ofthe material is measured after curing at 175° C. for 30 minutes. AsExample 1 includes blowing agent for expansion, lap shear testing isperformed with a sample having an initial thickness of about 1 mm and abond line of about 2 mm. During the curing at 175° C. for 30 minutes,the material expands and bonds to both metal pieces. Lap shear ismeasured at about 23° C., 90° C., 120° C., 150° C., 180° C., and 210° C.The test results are shown in Table 1.

Example 2 is prepared and tested the same as Example 1, except theamounts of some of the ingredients are changed.

Example 3 is prepared the same as Example 2, except the sample does notinclude the blowing agent or the zinc oxide, and the amount of thecalcium carbonate is increased. As there is no blowing agent, the bondline for the lap shear testing is set at the sample thickness, so thatthe material contacts both metal pieces.

Example 1, Example 2, and Example 3 are expected to have a heatdistortion temperature greater than 60° C. as measured according to ASTMD648 under a load of 1.8 MPa. After curing at 175° C. for 30 minutes,Example 1, Example 2, and Example 3 are expected to have a heatdistortion temperature greater than 160° C. as measured according toASTM D648 under a load of 1.8 MPa.

Comparative Example is prepared the same as Example 2, except the sampledoes not include the polysulfone and the core/shell polymer. Amounts ofother composition ingredients (including the amount of epoxy A, theaddition of epoxy D, and the amount of the calcium carbonate) are thusincreased. The Comparative Example loses most of its strength from 23°C. to 150° C. This material is not dry to the touch and cannot bepelletized.

TABLE 1 Comparative Example 1 Example 2 Example 3 Example CompositionWeight % Weight % Weight % Weight % Pigment 0.05 0.05 0.05 0.05 Epoxy A(Araldite GT 6097) 13.64 11.33 11.33 30.24 Polysulfone 18.90 18.90518.905 Epoxy D (Araldite GY282) 6.27 Masterbatch A 2.08 2.08 2.08 2.08Epoxy B (Araldite ECN 9699) 7.27 9.45 9.45 9.45 Epoxy C2 (Epalloy 8250)Epoxy C1 (Araldite EPN 9850) 28.36 28.355 28.355 28.35 Core/shellPolymer A (Kane Ace 267) 8.96 8.96 8.96 Calibrite OG 12.76 15.13 16.9817.78 Zinc Oxide (Extra R) 0.1 0.1 0.1 Dyhard 100S 5.53 3.29 3.29 3.32Omicure U52M 0.60 0.60 0.60 0.60 Genitron LE 1.75 1.75 1.75 Total 100.00100.00 100.00 100.00 Density (g/cm³) 1.27 1.26 1.31 1.26 Volumeexpansion of 25 mm × 25 mm × 1 mm specimen after 30 minutes at 175° C.Volume expansion percent 317 278 47 266 Lap Shear Properties at 23° C.(1.7 mm HDG, no oil, 25 × 25 × 2 mm) 1 mm thick material Maximum StressMPa 4.20 4.63 8.50 5.53 Cohesive Failure percent 100 (SCF) 100 (SCF) 100(SCF) 100 (CF) Lap Shear Properties at 90° C. (1.5 mm HDG no oil, 25 mm× 25 mm × 2 mm) 1 mm thick material) Maximum Stress MPa 3.73 3.27 7.875.10 Cohesive Failure percent 100% SCF 100% SCF 100% SCF 100% SCF LapShear Properties at 120° C. (1.5 mm HDG no oil, 25 mm × 25 mm × 2 mm) 1mm thick material) Maximum Stress MPa 2.68 3.18 6.91 3.31 CohesiveFailure percent 100 (SCF) 100 (SCF) 100 (SCF) (100 CF) Lap ShearProperties at 150° C. (1.5 mm HDG no oil, 25 mm × 25 mm × 2 mm) 1 mmthick material) Maximum Stress MPa 1.23 1.76 13.30 0.72 Cohesive Failurepercent 100 (SCF) 100 (SCF) 100 (CF/ 100 (CF) SCF) Lap Shear Propertiesat 180° C. (1.5 mm HDG no oil, 25 mm × 25 mm × 2 mm) 1 mm thickmaterial) Maximum Stress MPa 0.6 0.6 4.03 0.31 Cohesive Failure percent100 (CF)  100 (CF)  (AF) (CF) Lap Shear Properties at 210° C. (1.5 mmHDG no oil, 25 mm × 25 mm × 2 mm) 1 mm thick material) Maximum StressMPa 0.20 0.17 1.11 0.14 Cohesive Failure percent 100 (CF)  100 (CF) (100 CF)  100 (CF)  Tensile Properties of the uncured material, measuredat 23° C. (ISO 527) @ 100 mm/min Modulus MPa 133.11 124.34 280.75 8.39Maximum Stress MPa 5.73 4.52 4.91 0.194 Strain at failure percent 114.86182.48 109.91 >230 Tensile Properties of the cured material (cured at175° C. for 30 minutes) Tensile properties at 23° C. (ISO 527) @ 10mm/min Modulus MPa 623.04 348.13 1950.79 310.19 Maximum Stress MPa 8.316.24 32.7 4.53 Strain at failure percent 2.43 1.49 2.2 1.72 Tensileproperties at 150° C. (ISO 527) @ 10 mm/min Modulus MPa 83.92 61.02332.42 1.43 Maximum Stress MPa 2.37 2.5 11.5 0.286 Strain at failurepercent 23.15 17.98 21.26 19.45 DSC DSC Peak (° C.) 168.44 162.25 157.64164.74 DSC Onset (° C.) 154.4 147.18 146.49 144.80 DSC Enthalpy (J/g)251.4 244.40 210.00 246.40 Viscosity RPA at 90° C. 1.0 rad/s (kPa*s)7.28 7.06 7.36 1.46 9.1 rad/s (kPa*s) 2.02 2.19 2.68 0.19 100 rad/s(kPa*s) 0.53 0.58 0.73 0.04 DMA (1 × 10−5 m @ 40 Hz) E′ @ 23° C. MPa845.00 755.00 3310.00 783.00 E″ Max ° C. 122.90 130.90 130.90 118.40 Tandelta peak ° C. 149.6 & 151.6 & 148.90 149.80 193.1 186.9 SCF:superficiail cohesive failure CF: Cohesive failure AF: Adhesive failure

What is claimed is:
 1. A polymeric adhesive composition for molding orextruding an article comprising: i) about 25 to about 85 weight percentof one or more epoxy resins, based on the total weight of the polymericadhesive composition; ii) about 7 to about 45 weight percent of one ormore high temperature thermoplastic polymers, based on the total weightof the polymeric adhesive composition, having a glass transitiontemperature of about 175° C. or more; iii) about 0.5 to 15 weightpercent of one or more impact modifiers, wherein the impact modifiersincluding an elastomeric polymer core of a core/shell polymer; iv) oneor more curatives for curing the epoxy resin(s); and v) optionally up to40 weight percent of one or more fillers; and vi) optionally up to about7 weight percent of one or more blowing agents; wherein the one or moreepoxy resins includes one or more solid epoxy resins and one or moreliquid epoxy resins, wherein the concentration of the solid epoxy resinis sufficiently high so that the polymeric adhesive composition is asolid at room temperature.
 2. The polymeric adhesive composition ofclaim 1, wherein the one or more high temperature thermoplastic polymersincludes a polymer having a repeat unit with a sulfone group along thebackbone with two aryl sulfone linkages.
 3. The polymeric adhesivecomposition of claim 2, wherein the repeat unit includes one or moreether linkages.
 4. (canceled)
 5. The polymeric adhesive composition ofclaim 3, through wherein the concentration of the repeat unit is about90 weight percent or more, based on the total weight of the hightemperature thermoplastic polymer; and wherein the polymeric adhesivecomposition includes one or more polymeric fibers, wherein the length ofany fibers in the polymeric adhesive composition is about 50 mm or less.6. (canceled)
 7. The polymeric adhesive composition of any of claim 56,wherein the elastomeric polymer includes a polybutadiene, apolybutadiene copolymer, a random copolymer including two or moreα-olefins, a polyisoprene, or any combination thereof, or a blockcopolymer including a block thereof; wherein the elastomer polymer isprovided as discrete particles of a core/shell polymer.
 8. The polymericadhesive composition of claim 1, wherein the polymeric adhesivecomposition is a solid at a temperature of about 50° C., and thepolymeric adhesive composition has a tensile modulus of about 50 MPa ormore, as measured according to ISO 527, at about 23° C.; and the one ormore high temperature thermoplastic polymer has a melt flow rate fromabout 0.2 to about 100 g/10 min, as measured according to ASTMD D1238 at343° C./2.16 kg.
 9. The polymeric adhesive composition of claim 8,wherein the concentration of the high temperature thermoplastic polymeris sufficiently high so that the polymeric adhesive composition ischaracterized by a heat distortion temperature of about 60° C. or moreas measured according to ASTM D648 under a load of 1.8 MPa.
 10. Thepolymeric adhesive composition of claim 1, wherein the compositionincludes about 0.5 to 9 weight percent of the one or more impactmodifiers; and wherein the polysulfone is free of functional groups forreacting with epoxy.
 11. A pre-cure article including the polymericadhesive composition of claim 1, wherein the pre-cure article is anextruded article or a molded article.
 12. (canceled)
 13. (canceled) 14.(canceled)
 15. A post-cure article including a polymeric componentformed from curing the polymeric adhesive composition of claim 1,wherein the polymeric component includes a first surface attached to afirst metal component and a second surface attached to a second metalcomponent.
 16. The post-cure article of claim 15, wherein the post-curearticle has a thickness of about 0.3 mm to about 10 mm; the polymericcomponent has a glass transition temperature of about 150° C. or more;and the polymeric component is characterized by a heat distortiontemperature of about 120° C. or more as measured according to ASTM D648under a load of 1.8 MPa.
 17. (canceled)
 18. (canceled)
 19. A method ofpreparing a polymeric adhesive composition of claim 1, comprising thesteps of: mixing a polysulfone with one or more liquid epoxy resins toform a polysulfone/epoxy mixture; mixing at least the polysulfone/epoxymixture, the core/shell polymer including the elastomeric polymer, theone or more solid epoxy resins, a masterbatch including a polymericfiber and a liquid epoxy resin, and the curatives at a temperaturesufficiently low so that curing of the epoxy resin is substantiallyavoided and at a shear rate sufficiently low so that the particle sizeof the core/shell polymer is substantially maintained; forming apre-cure article; heating the pre-cure article so that the polymericadhesive composition cures into a cured polymeric component having afirst surface adhered to a first metal component and a second surfaceadhered to a second metal component.
 20. (canceled)
 21. A polymericadhesive composition for molding or extruding an article comprising: i)about 35 to about 65 weight percent of one or more epoxy resins,including a solid unmodified bisphenol-A based epoxy resin having anepoxide equivalent weight of about 800 g/equivalent or more as measuredaccording to ISO 3001, an epoxy cresol novolac resin having afunctionality of about 3.5 or more, and a liquid epoxy phenol novolacresin having an epoxy equivalent weight of about 150 to about 300g/equivalent as measured according to ISO 3001; ii) about 12 to about 30weight percent or more of one or more thermoplastic polysulfones havinga glass transition temperature of about 175° C. or more; iii) about 1 to9 weight percent of one or more impact modifiers including anelastomeric polymer core of a core/shell polymer; iv) about 2 to about 9weight percent of one or more curatives for curing the epoxy resin(s),wherein the one or more curatives includes a substituted urea; v) about5 to about 25 weight percent of one or more fillers selected from thegroup consisting of calcium carbonate, clay, silica, talc, glass, carbonor ceramic fibers, polymeric fibers, and any combination thereof; vi)about 0.1 to about 3 weight percent polyaramid fibers having an averagelength of about 35 mm or less; and vii) about 0.1 to about 3 weightpercent of one or more blowing agents; wherein the one or more epoxyresins includes one or more solid epoxy resins and one or more liquidepoxy resins, wherein the concentration of the solid epoxy resin issufficiently high so that the polymeric adhesive composition is a solidat room temperature having a tensile modulus at room temperature ofabout 20 MPa or more, as measured according to ISO
 527. 22. A devicecomprising: i) a first substrate; ii) one or more second substratesattached to the first substrate by: iii) a polymeric adhesive componentformed from the polymeric adhesive composition of claim 1, wherein thehigh temperature thermoplastic polymer has a glass transitionthermoplastic polymers of about 175° C. or more.
 23. The device of claim22, wherein the polymeric adhesive composition comprises: i) about 25 toabout 85 weight percent of one or more epoxy resins, based on the totalweight of the polymeric adhesive composition; ii) about 7 to about 45weight percent of one or more high temperature thermoplastic polymers(based on the total weight of the polymeric adhesive composition) havinga glass transition temperature of about 175° C. or more; iii) about 0.5to about 20 weight percent of one or more impact modifiers, wherein theimpact modifiers including an elastomeric polymer core of a core/shellpolymer; iv) one or more curatives for curing the epoxy resin(s) (e.g.,in an amount from about 0.4 to about 15 weight percent, based on thetotal weight of the polymeric adhesive composition); and v) optionallyup to 40 weight percent of one or more fillers; and vi) optionally up toabout 7 weight percent (e.g., from about 0.1 to about 4 weight percent)of one or more blowing agents; wherein the one or more epoxy resinsincludes the one or more solid epoxy resins and one or more liquid epoxyresins, wherein the concentration of the solid epoxy resin issufficiently high so that the polymeric adhesive composition is a solidat room temperature (e.g., the polymeric adhesive composition has atensile modulus of about 20 MPa or more, as measured according to ISO527 at about 23° C.).
 24. The device of claim 23, wherein the firstsubstrate is a cylindrical ring, and the second substrate is attached toan inside surface of the cylindrical ring.
 25. The device of claim 24,wherein the first substrate is a stator ring, and the one or more secondsubstrates are teeth each having a length aligned with an axis of thestator ring, and arranged for substantially or entirely covering aninner circumference of the stator ring.
 26. (canceled)
 27. (canceled)28. (canceled)
 29. (canceled)
 30. The device of claim 22, wherein i) thepolymeric adhesive component is in an expanded state including opencells and/or closed cells; and ii) the polymeric adhesive component hasa thickness from about 0.1 mm to about 10 mm.
 31. (canceled)
 32. Amethod of forming a device comprising the steps of: positioning a firstsubstrate relative to a second substrate so that a polymeric adhesivecomposition is interposed between the first and second substrates;heating the polymeric adhesive composition to a temperature of about150° C. or more for a sufficient time to cure the polymeric adhesivecomposition and form a cured polymeric adhesive component that adheresthe first substrate and the second substrate; wherein the polymericadhesive composition includes one or more solid epoxy resins and one ormore high temperature thermoplastic polymers having a glass transitiontemperature of about 175° C. or more.
 33. The method of 32, wherein thepolymeric adhesive composition comprises: i) about 25 to about 85 weightpercent of one or more epoxy resins, based on the total weight of thepolymeric adhesive composition; ii) about 7 to about 45 weight percentof one or more high temperature thermoplastic polymers (based on thetotal weight of the polymeric adhesive composition) having a glasstransition temperature of about 175° C. or more; iii) about 0.5 to about20 weight percent of one or more impact modifiers, wherein the impactmodifiers including an elastomeric polymer core of a core/shell polymer;iv) one or more curatives for curing the epoxy resin(s) (e.g., in anamount from about 0.4 to about 15 weight percent, based on the totalweight of the polymeric adhesive composition); and v) optionally up to40 weight percent of one or more fillers; and vi) optionally up to about7 weight percent (e.g., from about 0.1 to about 4 weight percent) of oneor more blowing agents; wherein the one or more epoxy resins includesthe one or more solid epoxy resins and one or more liquid epoxy resins,wherein the concentration of the solid epoxy resin is sufficiently highso that the polymeric adhesive composition is a solid at roomtemperature; wherein the one or more high temperature thermoplasticpolymers includes a polymer having a repeat unit with one or moresulfone groups along the backbone.
 34. (canceled)
 35. (canceled) 36.(canceled)
 37. (canceled)
 38. (canceled)
 39. (canceled)
 40. (canceled)41. (canceled)